WO2002010129A2 - Materials that can be structured, method for producing the same and their use - Google Patents

Abstract

The invention relates to low-molecular or polymeric organic materials wherein at least one H atom is replaced by a group of the formula (A), wherein R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, C4-C18 aryl, C2-C10 alkenyl, wherein one or more hydrogen atoms may be replaced by halogen, such a Cl and F, or CN, and wherein one or more non-neighboring C atoms may be replaced by -O-, -S-, -CO-, -COO-, -O-CO-, Z represents -O-, -S-, -CO-, -COO-, -O-CO- or a bivalent group -(CR1-R2)n-, wherein R1 and R2 independently represent hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group having 1 to 20 C atoms, C4-C18 aryl, C2-C10 alkenyl, wherein one or more hydrogen atoms may be replaced by halogen, such as Cl and F, or CN, and wherein one or more non-neighboring C atoms may be replaced by -O-, -S-, -CO-, -COO-, -O-CO-, X represents a bivalent group -(CR1R2)n- wherein R1 and R2 independently represent hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group heaving 1 to 20 C atoms, C4-C18 aryl, C2-C10 alkenyl, wherein one or more hydrogen atoms may be replaced by halogen, such as Cl and F, or CN, and n represents an integer between 1 and 20, preferably between 3 and 10, and particularly between 3 or 6, with the proviso that the number of the groups A is limited by the H atoms that are maximally available, that means that can be maximally substituted. The invention further relates to the use of said compounds for producing optionally multilayer structured light-emitting diodes, lasers, solar cells, waveguides or integrated circuits.

Description

description

Structurable materials, processes for their production and their use

For a few years now there has been a rapidly growing demand for organic materials which are required for use in electronics applications. Typical applications are those in organic (OLED) or polymeric light-emitting diodes (PLED) (see, for example, EP-A-0 676461, WO 98/27136), organic solar cells (see, for example, WO 98/48433, WO 94/05045), organic lasers (e.g. WO 98/03566) and also in organic circuits (ICs) (e.g. WO 95/31833, WO 99/10939).

The use of materials is the above. Applications and patents and the literature references cited therein are not described here. With regard to the use, these texts are considered via quotation as part of the present invention.

For use in the above Areas of application include both low molecular weight and polymeric compounds. Here, for the organic or polymeric light emitting diodes and laser applications, come both active materials (i.e. light-emitting substances) and materials for further auxiliary layers, i.e. H. for example charge transport layers with certain optical properties in question.

For use in the fields of application solar cells and organic switching elements, organic semiconductors or insulators are preferred, and thus i. d. R. Charge transport materials with different transport properties, required.

In all of these applications, conjugated or at least partially conjugated polymers are typically used in the field of high molecular weight compounds. Typical examples of conjugated polymers are poly- (p-phenylene-vinylene) [PPV] or poly-p-phenylene [PPP]. If the PPP structure predominantly Fluorene building blocks, these materials are also referred to as polyfluorenes. If the PPP structure predominantly contains spiro-9,9'-bifluorene units, this is also called poly-spiros.

Partially conjugated polymers in the sense of this invention are to be those substances which either have mainly conjugated segments in the main chain, which are interrupted by non-conjugated segments, or those which have longer conjugated segments in the side chain.

On the other hand, there are also low molecular weight compounds in some of the above. Areas of application already successfully in use.

Among the low molecular weight compounds, those with aromatic π systems (aromatics) have become particularly important. In addition to 2-dimensional aromatics such as Triphenylene derivatives (DE-A-4422332), in particular aromatics with a 3-dimensional, spatially extended structure, have proven to be advantageous. Typical representatives are compounds based on spirobifluorene (EP-A-676461), triptycene or Iptycen (DE-A-19744792).

There are already various types of substances for all of these applications

Find use, but the development of such compounds is by no means to be considered complete.

On the one hand, there is strong pressure, the operational life of the

To increase connections in the corresponding applications; on the other hand, the structuring of corresponding applications is also not solved

Problem.

The structuring is a very important criterion depending on the area of application: With displays (based on OLED or PLED technology), for example, the individual pixels must be created. A similar problem naturally arises in the production of organic circuits and in some cases also in the structuring of organic solar cell panels or laser arrays. These structures are usually carried out on the “feed lines”, that is to say, for example, on the electrodes. This can e.g. B. by Shadow masks are made in the manner of a template; However, this can result in significant disadvantages for industrial mass production: the masks are unusable after one or more uses due to the formation of deposits and have to be regenerated at great expense.

Another structuring option is to apply the active layer (here: either the light-emitting layer in OLEDs / PLEDs and lasers or charge transport layers in all applications) in a structured manner. Since this causes considerable problems, it is understandable from the dimensions alone: structures in the range from a few 10 μm with layer thicknesses in the range from approx. 100 nm to a few μm must be created. Printing processes (such as off-set printing, inkjet printing, or similar techniques) may be suitable for this, but no such process is really suitable for production yet. The mask technology already described above for the electrodes is also used here (in the field of OLEDs). However, this clearly brings with it the problems of deposit formation described above.

Made of polym. Materials, Science and Engineering 80, 122 (1999) are now known with N, N, N ', N ^' -tetraphenylbenzidines functionalized with oxetane groups, which can be crosslinked photo-induced. The aforementioned class of connections are used as structurable hole conductors in organic light-emitting diodes (OLEDs), so that structured OLEDs can be produced.

It was therefore an object of the present invention to provide structurable materials which are suitable for use in structured devices, such as OLEDs, PLEDs, organic lasers, organic switching elements, and organic solar cells, the property profile of these devices at least being retained.

It has now surprisingly been found that organic materials can be structured in the applications listed above if they contain at least one oxetane group capable of crosslinking, the crosslinking reaction of which can be triggered and controlled in a targeted manner. This can be done under suitable Conditions are carried out in such a way that the otherwise existing device characteristics are not impaired, but so that the structuring is significantly simplified or made possible in the first place.

The invention therefore relates to low molecular weight or polymeric organic materials which are used in the abovementioned electronic applications in which at least one H atom is replaced by a group of the formula (A)

(A) where

R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl, alkoxy or thioalkoxy group with 1 to 20 carbon atoms, C4-C18-aryl, C2-C10-alkenyl in which one or more hydrogens by halogen, such as Cl and F, or CN can be replaced and one or more non-adjacent C atoms can be replaced by -O-, -S-, -CO-, -COO-, -O-CO-,

Z for -O-, -S-, -CO-, -COO-, -O-CO- or a bivalent group - (CRιR ₂ ) _n - in which R1 and R2 independently of one another are hydrogen, a straight-chain, branched or cyclic alkyl -, Alkoxy, alkoxyalkyl or thioalkoxy group with 1 to 20 carbon atoms, C4-C18-aryl, C2-C10-alkenyl mean in which one or more hydrogens can be replaced by halogen, such as Cl and F or CN, and one or several non-adjacent C atoms can be replaced by -O-, -S-, -CO-, -COO-, -O-CO-,

X is a divalent group - (CRιR ₂ ) _n - in which R1 and R2 independently of one another hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group with 1 to 20 C atoms, C4-C18-aryl , C2-C10-alkenyl mean in which one or more hydrogens can be replaced by halogen, such as Cl and F or CN, and n denotes an integer between 1 and 20, preferably between 3 and 10, in particular 3 or 6, with the proviso that the number of these groups A is limited by the maximum available, ie substitutable, H atoms.

The electronic materials according to the invention are electroluminescent or laser materials such as

A) Homo- or copolymers based on PPV or poly-fluorene or poly-spiro

B) low molecular weight compounds with 3-dimensional spirobifluorene structure,

C) Low molecular weight compounds with 3-dimensional triptycene structure

D) Low molecular weight compounds with a 2-dimensional triphenylene structure

E) Derivatives of perylene-tetra-carboxylic acid diimide

F) Derivatives of quinaciridone

G) organic lanthanoid complexes

H) Derivatives of aluminum tris-quinoxalinate

I) oxadiazole derivatives or hole conductors such as

J) polystyrenes, polyacrylates, polyamides, polyesters which carry derivatives of tetra-aryl-benzidine in the side chain, K) low molecular weight compounds with a 2-dimensional triphenylene structure or around electron conductors such as L) derivatives of aluminum tris-quinoxalinate M) oxadiazole derivatives

The oxetane content is defined by the molar ratio of oxetane rings based on the total of organic rings, i.e. including the oxetane rings in the respective structure. This can generally be determined by analytical methods. One of the preferred methods besides IR spectroscopy is nuclear magnetic resonance spectroscopy (NMR).

Rings in the sense of the invention are cyclic structural elements formed from at least three ring atoms with the proviso that at least two carbon atoms are included (The Ring Index, Patterson and Capell, Reinhold Publishing Company, 1940 and Handbook of Chemistry and Physics, 62 ^πd ed. 1981, C-48).

The oxetane content can be varied within a wide range from 0.01 to 0.6. In the lower area, low degrees of cross-linking are achieved, which result in relatively soft, rubber-elastic to gel-like layers. In the upper one, high crosslinking densities are achieved with thermoset properties, e.g. Bakelite.

A1) The homo- and copolymers of the PPV contain one or more structural units of the formula (B), at least one H atom in the polymer being replaced by a substituent of the formula (A).

(B)

The substituents R to R """are the same or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, one or more non-adjacent CH ₂ groups passing through -O-, -S-, -CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A ^" , or -CONR ⁴ - can be replaced and wherein a or more H atoms can be replaced by F, or an aryl group having 4 to 14 C atoms, which can be substituted by one or more non-aromatic radicals R '.

R1, R2, R3, R4 the same or different aliphatic or aromatic

Hydrocarbon residues with 1 to 20 carbon atoms or also H.

A-: a single charged anion or its equivalent;

PPVs according to WO 98/27136, which are shown in formula (C), are preferred.

(C) where the symbols and indices have the following meanings:

Aryl: an aryl group with 4 to 14 C atoms;

R \ R ": identical or different, a straight-chain or branched or cyclic alkyl or alkoxy group with 1 to 20 C atoms, one or more non-adjacent CH ₂ groups being represented by -O-, -S-, -CO-, - COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A-, or -CONR ⁴ - can be replaced and one or more H atoms can be replaced by F, CN, F, Cl or an aryl group with 4 to 14 C atoms, which can be substituted by one or more non-aromatic radicals R ';

R ¹ , R ² , R ³ , R ^{4 are the} same or different aliphatic or aromatic

Hydrocarbon residues with 1 to 20 carbon atoms or also H.

A ^" : a single charged anion or its equivalent; m: 0, 1 or 2; n: 1, 2, 3, 4 or 5.

Polymers consisting mainly of repeating units of the formula (C) are particularly preferred.

Also very particularly preferred are copolymers consisting essentially of, particularly preferably consisting of repeating units of the formula (I) and further repeating units, which preferably also have poly (arylene vinylene) structures, particularly preferably 2,5-dialkoxy-1,4- contain phenylene vinylene structures, the alkoxy groups preferably being straight-chain or branched and containing 1 to 22 carbon atoms.

Copolymers in the sense of the invention include statistical, alternating, regular and block-like structures.

Likewise preferred are polymers containing repeating units of the formula (C) in which the symbols and indices have the following meanings:

Aryl is phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or

4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl,

2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl,

2- or 3-furanyl and 2- (1, 3,4-oxadiazol) yl; R 'is the same or different, CN, F, Cl, CF ₃ or a straight-chain or branched alkoxy group with 1 to 12 C atoms; R ", the same or different, is a straight-chain or branched alkyl or

Alkoxy group with 1 to 12 carbon atoms; n is 0, 1, 2 or 3, particularly preferably 0, 1 or 2.

The production of such polymers is described in detail in WO 98/27136. Corresponding polymers according to the invention can be prepared by polymerizing corresponding monomers which carry the oxetane grouping of the formula (A).

A2) The homo- and copolymers of polyfluorene contain one or more structural units of the formula (D), at least one H atom in the polymer being replaced by a substituent of the formula (A).

Die Substituenten R' bis R"" sind dabei gleich oder verschieden H, CN, F, Cl oder eine geradkettige, verzweigte oder cyclische Alkyl- oder Alkoxygruppe mit 1 bis 20 C-Atomen, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch -O-, -S-, - CO-, -COO-, -O-CO-, -NR¹-, -(NR²R³)⁺-A^_, oder -CONR⁴- ersetzt sein können und wobei ein oder mehrere H-Atome durch F ersetzt sein können, oder eine Arylgruppe mit 4 bis 14 C-Atome, die durch einen oder mehrere, nicht aromatische Reste R' substituiert sein kann. R¹,R²,R³,R⁴ gleich oder verschieden aliphatische oder aromatische

The substituents R 'to R "" here are identical or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, one or more non-adjacent CH ₂ groups passing through -O-, -S-, - CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A ^_ , or -CONR ⁴ - can be replaced and where a or more H atoms can be replaced by F, or an aryl group having 4 to 14 C atoms, which can be substituted by one or more non-aromatic radicals R '. R ¹ , R ² , R ³ , R ^{4 are the} same or different aliphatic or aromatic

Hydrocarbon radicals with 1 to 20 carbon atoms or also H. A ^" : a simply charged anion or its equivalent; n, m: 0, 1, 2 or 3, preferably 0 or 1.

A2.1) Structures according to DE-A-19846767 which are listed below are preferred. In addition to structural units of the formula (E1), these polymers contain

worin

wherein

R ¹ , R ^{2 are} identical or different hydrogen, -CC ₂₂ alkyl, C2-Q_o-heteroaryl, C ₅ -C20 aryl, F, Cl, CN; where the alkyl radicals mentioned above can be branched or unbranched or also represent cycloalkyls, and individual, non-adjacent CH ₂ groups of the alkyl radical by O, S, C = 0, COO, NR ⁵ or also C ₂ -C ₀ -aryl or Heteroaryls can be replaced, wherein the above-mentioned aryls / heteroaryls can be substituted with one or more non-aromatic substituents R ³ . Preferred are compounds in which R ¹ and R ^{2 are} both the same and are not hydrogen or chlorine; further preferred are compounds in which R ¹ and R ² are different from one another and also different from hydrogen; R ³ , R ^{4 are the} same or different H, -CC ₂₂ alkyl, C ₂ -C ₂ o-heteroaryl, C ₅ -C ₂ o-aryl, F, Cl, CN, S03R ⁵ , NR ⁵ R ⁶ ; the alkyl radicals can be branched or unbranched or can also be cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or C ₂ -C ₁₀ aryls or heteroaryls, the above-mentioned aryls / heteroaryls having one or more non-aromatic substituents R ³ can be substituted,

R ⁵ , R ^{6 are the} same or different H, -CC ₂₂ alkyl, C ₂ -C ₂₀ heteroaryl, C ₅ -C ₂ o-aryl; the alkyl radicals can be branched or unbranched or can also be cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or also C ₂ -C ₁₀ aryls, the above-mentioned aryls being substituted by one or more nonaromatic substituents R ³ can be, and m, n is in each case an integer 0, 1, 2 or 3, preferably 0 or 1,

structural units of the formula (E2)

(E2) worin

(E2) in which

Ar ¹ , Ar ^{2 are} mono- or polycyclic aromatic conjugated systems with 2 to 40 carbon atoms, in which one or more carbon atoms can be replaced by nitrogen, oxygen or sulfur, and which can be substituted by one or more substituents R ³ . It is entirely possible or in some cases even preferred that the aromatics Ar ¹ and Ar ² are linked to one another by a bond or a further substituted or unsubstituted carbon atom or hetero atom and thus form a common ring.

R ^{7 the} same or different -CC ₂₂ alkyl, C ₂ -C ₂ o-heteroaryl or C ₅ -C ₂ o-aryl; the alkyl radicals can be branched or unbranched or can also be cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical are replaced by O, S, C = 0, COO, NR ⁵ or simple aryls be, wherein the above-mentioned aryls / heteroaryls may be substituted with one or more non-aromatic substituents R ³ .

The structural units of the formula (E2) are very particularly preferably derived from the following main bodies:

Diphenylamine derivatives which are incorporated in the 4,4'-position in the polymer;

Phenothiazine or phenoxazine derivatives, which are incorporated in the polymer in the 3,7 position;

Carbazole derivatives which are incorporated into the polymer in the 3,6-position;

Dihydrophenazine derivatives which are incorporated into the polymer in the 2,6- or 2,7-position;

Dihydroaciridine derivatives which are incorporated in the polymer in the 3,7 position.

A2.2) Structures according to DE-A-19846766, which are listed below, are also preferred. These polymers contain structural units of the formula (F)

R ⁱ R ²

(F) where

R ¹ , R ^{2 represent} two different substituents from the group C ₂ -C ₄ o-aryl or heteroaryl; wherein the aforementioned aryls or heteroaryls can be substituted with one or more substituents R ³ ; The aryls or heteroaryls in the sense of this invention should already be different if they differ in the type or position of substituents,

R ³ , R ^{4 are the} same or different -CC ₂₂ alkyl, C ₂ -C ₂ o-aryl, F, Cl, CN, S0 ₃ R ⁵ , NR ⁵ R ⁶ ; the alkyl radicals can be branched or unbranched or can also be cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical are replaced by O, S, C = 0, COO, NR ⁵ or simple aryls can be, where the abovementioned aryls can be substituted by one or more nonaromatic substituents R ³ ,

R ⁵ , R ^{6 are the} same or different H, CrC ₂₂ alkyl, C ₂ -C ₂ o-aryl; the

Alkyl radicals can be branched or unbranched or also represent cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or simple aryls, where the abovementioned aryls can be substituted by one or more nonaromatic substituents R ³ , and m , n is an integer 0, 1, 2 or 3, preferably 0 or 1.

R ¹ , R ² very particularly preferably represent two different substituents from the group C ₅ -C o-aryl, C ₂ -C o heteroaryl; wherein the above-mentioned aryls or heteroaryls can be substituted with one or more substituents R ³ .

A2.3) Structures according to DE 19846768.0, which are listed below, are also preferred. These are polyfluorenes, which in addition to units according to formula (E1)

(E1) in which

R ¹ , R ^{2 are} identical or different hydrogen, -CC ₂₂ alkyl, C ₂ -C ₂₀ -A17I or -

Heteroaryl, F, Cl, CN; wherein the alkyl radicals mentioned above can be branched or unbranched or also represent cycloalkyls, and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or simple aryls, the above mentioned aryls can be substituted with one or more substituents R ³ . Compounds are preferred in which R ¹ and R ^{2 are} both the same and are not hydrogen or chlorine. Are also preferred Compounds in which R ¹ and R ² are different from one another and also different from hydrogen;

R ³ , R ^{4 are} identical or different C ₁ -C ₂₂ alkyl, C ₂ -C ₂ o-aryl or heteroaryl, F, Cl, CN, SO ₃ R ⁵ , NR ⁵ R ⁶ ; the alkyl radicals can be branched or unbranched or can also be cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or else simple aryls, where the abovementioned aryls can be substituted by one or more nonaromatic substituents R ³ ,

R ⁵ , R ^{6 are the} same or different H, CrC ₂₂ alkyl, C ₂ -C ₂ o-aryl; the

Alkyl radicals can be branched or unbranched or also represent cycloalkyls; and individual, non-adjacent CH ₂ groups of the alkyl radical can be replaced by O, S, C = 0, COO, NR ⁵ or simple aryls, where the abovementioned aryls can be substituted by one or more nonaromatic substituents R ³ , and m , n is an integer 0, 1, 2 or 3, preferably 0 or 1, in any case still structural units of the formula (G1)

(G1) contain, wherein

Ar (omat) is a mono- or polycyclic aromatic conjugated system with 5 to 20 carbon atoms, in which one or more carbon atoms can be replaced by nitrogen, oxygen or sulfur, and the linking points of which are chosen such that an angle unequal along the polymer main chain 180 °, preferably less than 120 °, particularly preferably less than 90 °.

Polymers containing at least 1 mol%, preferably 2 mol% to 50 mol%, of structural units (one or more different) of the structural unit (G1) are particularly preferred here.

The production of such polymers is described in detail in DE-A-19846767, DE-A-19846766 and DE-A-19846768. The production of corresponding Polymers according to the invention can be carried out by polymerizing in corresponding monomers which carry the oxetane grouping.

A3) The homo- and copolymers of the poly-spiro contain one or more structural units of the formula (H), at least one H atom in the polymer being replaced by a substituent of the formula (A).

(H) The substituents R 'to R "" here are identical or different H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, one or more non-adjacent CH ₂ -Groups can be replaced by -0-, -S-, - CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A ^" , or -CONR ⁴ - and wherein one or more H atoms can be replaced by F, or an aryl group having 4 to 40C atoms, which can be substituted by one or more non-aromatic radicals R '. R ¹ , R ² , R ³ , R ⁴ the same or different aliphatic or aromatic

Hydrocarbon radicals with 1 to 20 carbon atoms or also H. A ^" : a simply charged anion or its equivalent; n, m, o, p 0, 1, 2, or 3, preferably 0.1 or 2.

Preferred embodiments of the poly-spiros are contained in (US-A-5621131).

The preparation of such polymers is described in detail in US-A-5621131.

Corresponding polymers according to the invention can be prepared by polymerizing corresponding monomers which carry the oxetane grouping.

B) The low molecular weight compounds with a 3-dimensional spirobifluorene structure consist of structural units of the formula (11)

(11) where the benzo groups can be substituted and / or fused independently of one another and wherein at least one H atom is replaced by a substituent of the formula (A).

Compounds according to EP-A-0676461, as represented in formula (12), are preferably used here,

(12)

where the symbols and indices have the following meanings: K, L, M, N are the same or different

R, identical or different, has the same meanings as K, L, M, N or is -H, a linear or branched alkyl, alkoxy or

Ester group with 1 to 22 carbon atoms, -CN, -N0, -NR ² R ³ , -Ar or -O-Ar;

Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can carry one or two radicals R, m, n, p are 0, 1, 2 or 3; X, Y are the same or different CR, N;

Z is -O-, -S-, -NR ¹ -, -CR ¹ R ⁴ -, -CH = CH-, -CH = N-;

R ¹ , R ⁴ , the same or different, can have the same meanings as R.

R ² , R3 are the same or different H, a linear or branched

Alkyl group with 1 to 22 carbon atoms, -Ar, 3-methylphenyl.

The preparation of such compounds is described in detail in EP 676461. Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms with the oxetane grouping according to formula (A).

C) The low molecular weight compounds with a 3-dimensional triptycene structure consist of structural units of the formula (J)

(J) where the benzo groups can be substituted and / or fused independently of one another and where at least one H atom is replaced by a substituent of the formula (A).

Compounds according to DE-A-19744792 are preferably used here. The preparation of such compounds is described in detail in DE-A-19744792. Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms with the oxetane grouping according to formula (A).

D) The low molecular weight compounds with a 2-dimensional triphenylene structure consist of structural units of the formula (K)

(K) where the benzo groups can be substituted and / or fused independently of one another, at least one H atom being replaced by a substituent of the formula (A).

Compounds according to DE-A-4422332 are preferably used here. The preparation of such compounds is described in detail in DE-A-4422332. Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms with the oxetane grouping according to formula (A). E) The derivatives of perylene tetracarboxylic acid diimide consist of structural units of the formula (L)

(L) where the benzo groups can be substituted independently of one another and where at least one H atom is replaced by a substituent of the formula (A).

Analogously to R ', R ", these substituents can, in the same or different way, represent a straight-chain, branched or cyclic alkyl or alkoxy group with 1 to 20 carbon atoms.

Atoms, where one or more non-adjacent CH ₂ groups by -O-, -S-, -

CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A ^_ , or -CONR ⁴ - can be replaced and one or more H atoms can be replaced by F. can, or an aryl group with 4 to 14 carbon atoms, which can be substituted by one or more, non-aromatic radicals R '. Furthermore, those other than R 'and R "can

Substituents also mean CN, F and Cl.

Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms with the oxetane grouping according to formula (A).

F) The derivatives of quinaciridone consist of structural units of the formula (M)

(M) where the benzo groups can be substituted independently of one another and where at least one H atom is replaced by a substituent of the formula (A).

Analogously to R ', R ", the substituents can be identical or different to a straight-chain, branched or cyclic alkyl or alkoxy group having 1 to 20 C atoms, one or more non-adjacent CH ₂ groups being represented by -0-, -S- , - CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A-, or -CONR ⁴ - can be replaced and where one or more H atoms by F may be replaced, or an aryl group with 4 to 14 carbon atoms, which may be substituted by one or more non-aromatic radicals R '. Furthermore, the substituents different from R and R "can also mean CN, F and Cl.

Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms with the oxetane grouping according to formula (A).

G) The organic lanthanoid complexes consist of structural units of the formula (N)

LnR ' _n

(N)

The substituents R 'can be the same or different carboxylates, ketonates, 1, 3-

Diketonates, imides, amides, alcoholates, where at least one H atom is replaced by a substituent according to formula (A).

The number of ligands depends on the metal. The organic complexes of europium, gadolinium and terbium are preferred here, particularly preferably those of the europium. Corresponding compounds according to the invention can be prepared by replacing corresponding substituents or H atoms in the substituents by the oxetane grouping of the formula (A).

H) The derivatives of metal quinoxalinate consist of structural units of the formula (O)

(O) where the benzo groups can be substituted independently of one another by radicals R ^' ,

M stands for aluminum, zinc, gallium, indium, preferably aluminum; n stands for an integer 0, 1, 2 or 3.

The substituents of the benzo group R 'may be the same or different, a straight-chain, branched or cyclic alkyl or alkoxy group with 1 to 20 C-

Atoms, where one or more non-adjacent CH ₂ groups by -O-, -S-, -

CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A-, or -CONR ⁴ - can be replaced and one or more H atoms can be replaced by F. can, or an aryl group with 4 to 14 carbon atoms, which can be substituted by one or more, non-aromatic radicals R '. Furthermore, those of R 'and R "different

Substituents also mean CN, F and Cl.

The oxetane group according to formula (A) according to the invention can now either be an H

Replace atom on one of the quinoxaline rings or on another ligand

R ^' , which replaces one of the quinoxaline ligands. I) The derivatives of oxadiazole consist of structural units of the formula (P)

(P) where Ar 'and Ar "can be identical or different to a substituted or unsubstituted aromatic or heteroaromatic having 4 to 14 C atoms, at least one H atom being replaced by a substituent of the formula (A).

Ar 'and Ar "are preferably identical or different phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5 -Pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl.

The possible substituents are the same or different, CN, F, Cl, CF ₃ or a straight-chain, cyclic or branched alkyl or alkoxy group with 1 to 12 carbon atoms, one or more non-adjacent CH ₂ groups being denoted by -O-, -S-, - CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A ^" , or -CONR ⁴ - can be replaced and where one or more H- Atoms can be replaced by F.

The oxetane group according to formula (A) according to the invention can now either replace an H atom on one of the aryl rings or can also sit on one of the substituents of the aryl rings.

J) Polymers (polystyrenes) carrying tetraaryl-benzidine units in the side chain consist of structural units of the formula (Q) or analogous compounds in other polymer backbones (polyacrylates, polyamides, polyesters)

(Q) where Ar ', Ar ", Ar"' and Ar "" may be identical or different to a substituted or unsubstituted aromatic or heteroaromatic having 4 to 14 carbon atoms

Ar ", Ar", Ar '"and Ar" "are preferably identical or different phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl.

The possible substituents are the same or different, CN, F, Cl, CF ₃ or a straight-chain, cyclic or branched alkyl or alkoxy group with 1 to 12 carbon atoms, one or more non-adjacent CH ₂ groups being denoted by -O-, -S-, - CO-, -COO-, -O-CO-, -NR ¹ -, - (NR ² R ³ ) ⁺ -A-, or -CONR ⁴ - can be replaced and where one or more H- Atoms can be replaced by F.

This tetraaryl-benzidine group is now connected to the main polymer chain via a spacer, preferably a C1 to C6 alkyl, alkoxy or ester group.

The oxetane group according to formula (A) according to the invention can now either replace an H atom on one of the aryl rings, or sit on one of the substituents of the aryl rings, or also on another polymerized monomer which does not carry a tetraaryl-benzidine unit.

The substances described above can now be used as a pure substance or as a mixture with one another or also with other auxiliary substances. The invention further relates to mixtures or formulations comprising the materials according to the invention and added auxiliaries, such as initiators, and, if appropriate, sensitizers, stabilizers, retarders, inhibitors, reactive thinners, etc.

At least one photoinitiator or photoinitiator system is admixed to the materials according to the invention. The concentration is typically selected in the range from 0.1 to 1.0% by weight, based on the compound / polymer according to the invention. Irradiation with actinic radiation generates an acid which triggers a crosslinking reaction through cationic ring-opening polymerization.

A pattern of areas with cross-linked and areas with non-cross-linked material can be obtained by structured irradiation. The areas with uncrosslinked material can then be removed by suitable operations (e.g. rinsing with suitable solvents). This leads to the desired structuring.

If cross-linking of larger areas is desired, the cross-linking can be initiated by applying an acid after film formation.

Another advantageous effect according to the invention is that the crosslinking increases the mechanical and thermal stability of the layers produced using the materials according to the invention. The result of this is that the devices which contain — crosslinked — materials according to the invention are significantly more durable under corresponding conditions (for example thermal stress, mechanical stress). This effect is more pronounced the higher the degree of crosslinking.

As a result, the subsequent application of the various layers after crosslinking has taken place. For example, an already cross-linked layer can be used as a substrate for separating further substances from the liquid phase. The layer structure achieved in this way can be used as a waveguide if materials with different optical refractive indices are specifically selected. The emitter from the solution is preferably applied to an already crosslinked layer of a hole conductor or electron conductor. With the aid of the materials according to the invention, it is possible to produce multilayer devices using soluble active materials.

The structuring takes place - as described above - by irradiation. This is a standard process in today's electronics industry and can be carried out, for example, by irradiation with lasers or by area irradiation through an appropriate mask. In contrast to the disadvantageously described above, this mask poses no risk of occupancy, since only radiation and no material flow through the mask can be recorded here.

Lateral positioning is possible in the case of the laser as a source either by moving the substrate, the light source itself or by optical aids. A possible tool for moving the substrate is an XY table which is driven by stepper motors. Optical aids can be mirrors. Structuring using a shadow mask is particularly easy and quick, using a flat light source, e.g. a high pressure mercury lamp is irradiated.

The invention further relates to the layers which are formed by crosslinking.

The invention thus also relates to a structured organic electronic device, in the sense of this invention, with one or more active layers, at least one of these active layers being produced from one or more materials of the formula (A) according to the invention.

The general structure for devices of this type is described above;

(i) OLEDs and PLEDs analogous to EP 676 461 and WO 98-27136 and the literature cited therein, (ii) organic solar cells analogous to WO 94-05045 and WO 98-48433 and the literature cited therein, (iii) organic lasers analogous to WO 98 -03566 and the literature cited therein. (iv) Organic circuits (ICs) analogous to WO 95-31833 and WO 99-10939 and the literature cited therein.

The invention is explained in more detail by the following examples, without wishing to restrict it thereby.

Part A: Synthesis of the Monomers: Monomers for Units According to Formula (D) (Fluorenes)

Example M1: Preparation of 9- (2,5-dimethylphenyl) -9- (4-oxymethylene {2 - [(3-ethylyloxetane) -3-yl)} phenyl) -2,7-dibromofluorene (M1)

In a 50 ml four-necked flask, 808 mg (6 mmol) of 2-ethyl-2-chloromethyloxetane (see Chemphyschem. 2000, 207), 345 mg (5.2 mmol) of KOH (85%) 2.60 g (5 mmol) of 9- (2nd , 5-Dimethylphenyl) -9- (4-hydroxyphenyl) -2,7- dibromofluorene (see WO 00/22026) carefully mixed with KOH and heated to 150 ° C. Then another three portions of 808 mg (6 mmol) of 2-ethyl-2-chloromethyloxetane were added over two hours and the mixture was stirred at this temperature for a further 2 h. The reaction was followed by TLC (hexane / CHCI ₃ 1: 1).

The reaction mixture was cooled and 50 ml of water were added at room temperature. Then ethyl acetate (50 ml) was added. A white solid precipitated out and did not dissolve in either the aqueous or the organic phase. It was sucked off. After drying in vacuo, 2.2 g (3.55 mmol, 71%) of the monomer M1, which was ¹ H NMR> 99%, was obtained.

¹ H NMR (benzene-de, 400 MHz): 7.72 (dd, 2 H, J = 2.0, 0.8, fluorene H1 / H8); 7.28 (dd, 2H, J = 2.0, 7.8, fluorene H3 / H6); 7.21 (br. S, 1 H, H-6 "phenyl); 7.06 (d with Fs., 4 H, J = 8.0 Hz, H-phenyl); 6.88-6.80 (m, 2 H, H3", H4 "); 6.47 (d with Fs., 2 H, j, 7.7 Hz, Fluorene H4 / H5), 4.35 (d, J = 7.2 Hz, 2 H oxetane); 4.25 (d, J = 7.0 Hz, 2 H oxetane) ; 3.55 (s, 2H, OCH ₂ ); 2.01 (s, 3H, CH ₃ ); 1.55 (q, 2H, J = 6.8 Hz, CH ₂ -ethyl); including at 1.54 (s, 3H, CH ₃ ); 0.61 (t, J = 6.8 Hz, CH ₃ ethyl). Example M2: Preparation of 9- (2,5-dimethylphenyl) -9- {6 - [(3-methyloxetane) -3-yl) methoxy] hexoxy} -2,7-dibromofluorene (monomer M2)

Analogously to Example M1, 2.22 g (5 mmol) of 9- (2,5-dimethylpehnyl) -9-hydroxy-2,7-dibromofluorene (see WO 00/22026) with 2.65 g (2 eq) (6'-bromohexyloxy-3 -methyl) -3-methyloxetane (see Polym. J. 1993; 25, 1283) at 50 ° C for 23 h. This gave 2.04 g (3.25 mmol, 65%) of the monomer M2, which was ¹ H NMR> 98%.

¹ H NMR (CDCI ₃ , 400 MHz): 7.50 2 (brs, 7 H, fluorene-H, H6); 7.06 (d, 1H, J = 8.0 Hz, H-3 '); 6.88 (d, 1H, J = 8.0 Hz, H-4 '); 4.38 (d, J = 7.2 Hz, 2 H oxetane); 4.22 (d, J = 7.0 Hz, 2 H oxetane); 3.63 (m, 4H, OCH _2); 2.88 (s, 2H, OCH _2); 2.31 (s, 3H, CH _3); 1.78-1.20 (m, 14 H, 4 x CH ₂ , 2 x CH ₃ ).

Example M3: Preparation of 9,9-bis {6 - [(3-methyloxetane) -3-yl) methoxy] hexoxy} -2,7- dibromofluorene (M3)

1.44 g (60 mmol) NaH were suspended in 50 mL dry toluene and 50 mL dry DMA in a 250 mL single-necked flask with a reflux condenser. 3.24 g (10 mmol) of 2,7-dibromofluorene and 5.57 g (21 mmol) of (6'-bromohexyloxy-3-methyl) -3-methyloxetane were added to this reaction mixture and the mixture was heated at 100 ° C. for 1 hour. After cooling to room temperature, 1 mL H ₂ O was carefully added using a pipette and then 150 mL Et ₂ 0 was added. The organic phase was washed with 4 x 50 mL H ₂ 0, then dried with MgS0 and the solvents removed in vacuo. The pure product was obtained by column chromatography (2-fold) on silica gel with a mobile phase mixture of ethyl acetate: petroleum ether = 1: 2. Yield: 3.78 g (39%) viscous oil. ¹ H-NMR (CDCI ₃ , 300 MHz): 0.65 (m, 4 H), 1.09 (m, 4 H), 1.27 (s, 6 H), 1.40 (m, 4 H), 1.89 (m, 4 H) ), 3.34 (t, J = 6.6 Hz, 4 H), 3.40 (s, 4 H), 4.31-4.47 (AA'BB 'system, J = 5.7 Hz, 8 H), 7.43-7.51 (AA'BB 'System, J = 8.1 Hz, 4 H), 7.43 (m, 2 H). 13C-NMR (CDCI3, 75 MHz): δ = 21.4 (CH3), 24.0 (CH2), 26.1 (CH2), 29.8 (CH2), 30.0 (CH2), 40.3 (C _quart ), 40.5 (CH2), 56.0 ( C _qU art), 71.9 (CH ₂ ), 76.4 (CH ₂ ), 80.6 (CH2), 121.6 (CH), 121.9 (CH), 126.5 (CH), 130.6 (C _quart ), 139.5 ( _Cq u _a r) , 152.8 (C _qua rt). MS (70 eV, m / z (%)): 692 (M +, 100), 690 (50), 662 (12), 614 (12), 612 (11), 349 (14), 323 (30), 245 (10), 243 (10), 85 (38), 55 (23). IR (film, KBr): = 3048 cm ^-1 , 2931, 2860, 2797, 1598, 1570, 1450, 1416, 1398, 1378, 1264, 1117, 1061, 1004, 979, 940, 878, 835, 811, 741 666, 427. UV / vis (CHCI ₃ ) λ _ma χ (ε) = 282 nm (26178), 303 nm (14170), 314 nm (18116). C ₃₅ H ₄₈ Br ₂ 0 ₄ (692.58): Calc .: C: 60.70, H: 6.99, Br: 23.07, Found: C: 61.24, H: 6.83, Br: 22.77.

Example M4: Representation of monomer M4 (see scheme 1)

M4 was prepared analogously to M1 with 2.2 eq (6'-bromohexyloxy-3-methyl) -3-methyloxetane. After working up analogously, 56% M4 was obtained as colorless

Solid.

The structures of the monomers M1-M4 used according to the invention and further monomers are summarized in Scheme 1:

Scheme 1: The preparation of the monomers M5-M11 not according to the invention is described in the unpublished application DE 10114477.6. Part B: Preparation of the polymers

Example P1: Copolymerization of monomer M1, 2,7-dibromo-9- (2 ', 5'-dimethylphenyl) -9- [3 ", 4" -bis (2-methyl-butyloxy) phenyl] fluorene (M9 ), N, N'-bis (4-bromophenyl) -N, N'-bisphenylbenzidine (M10) and 9- (3,7-dimethyloctyloxyphenyl) -9- (2,5-dimethylphenyl) fluorene-2,7 -pinacolybisbisboronic acid (M8) by Suzuki reaction (polymer P1).

1.6237 g (2.400 mmol) 2,7-dibromo-9- (2 ', 5 ⁱ -dimethylphenyl) -9- [3 ", 4" -bis (2-methylbutyloxy) phenyl] fluorene (M9), 4.5281 g (6.00 mmol) 9- (3,7-dimethyloctyloxyphenyl) - 9- (2,5-dimethylphenyl) fluorene-2,7-bisboronic acid pinacoyl ester (M8), 0.7757 g (1,200 mmol) N, N'-bis (4th -bromophenyl) -N, N'-bis (phenyl) benzidine (M10), 1.4842 g (2.400 mmol) monomer M1, 5.80 g (25.2 mmol) K ₃ P0 ₄ -H ₂ 0, 18 ml toluene, 9 ml water and 0.15 ml of ethanol was degassed for 30 min by passing N ₂ through it. Then 57 mg (0.05 mmol) Pd (PPh ₃ ) ₄ was added under protective gas. The suspension was stirred vigorously under an N ₂ blanket at an internal temperature of 87 ° C. (slight reflux). After 4 days, a further 0.10 g of 9- (3,7-dimethyloctyloxyphenyl) -9- (2,5-dimethylphenyl) fluorene-2,7-bisboronic acid pinacoyl ester was added. After heating for a further 6 hours, 0.3 ml of bromobenzene were added and the mixture was heated under reflux for a further 3 hours.

The reaction solution was diluted with 200 ml of toluene, the solution was stirred with 200 ml of 2% aqueous NaCN for 3 h. The mixture lightened almost completely. The organic phase was washed with H ₂ 0 and precipitated by adding 800 ml of ethanol. The polymer was dissolved in 200 ml of chloroform at 40 ° C. for 1 hour, filtered through Celite and precipitated with 250 ml of MeOH, washed and dried in vacuo. In 200 ml of THF / 250 ml of methanol was reprecipitated again, suction filtered and dried to constant mass. 4.80 g (9.64 mmol, 80%) of the polymer P1 were obtained as a slightly yellow solid. ¹ H NMR (CDCI ₃ ): 7.9-6.6 (m, fluorene-H, phenyl-H); 4.52 and 4.43 (2 xd, J ~ 8Hz, 0.4 H each, oxetane H); 4.0-3.4 (3 xm, OCH ₂ ), 2.20 (s, CH ₂ ethyl, aroma CH ₃ ); 1.9-0.7 (m, alkyl H).

GPC: THF; 1 ml / min, PLgel 10μm Mixed-B 2 x 300 x 7.5 mm ² , 35 ° C, Rl detection: Mw = 77000 g / mol, Mn = 32000 g / mol. Other polymers were presented analogously to the descriptions for P1. The chemical properties are summarized in the following table. Some comparative polymers without oxetane units were also shown. These are also listed in the table. All of these polymers have also been studied for use in PLEDs. On the one hand, how PLEDs can be represented has already been explained above and is described in more detail in part C. The most important device properties (color, efficiency) are also listed in the table. In the case of the polymers P1-P9, the chemical and electro-optical data of the uncrosslinked polymers are shown. Networking is also described in Part C.

Table 1: Important characteristics of the investigated polymers

GPC measurements THF; 1 ml / min, PIgel 10μm Mixed-B 2 x 300 x 7.5 mm ² , 35 ° C, Rl detection was calibrated against polystyrene * For the production of the polymer LEDs, see part C

Part C: Production and Characterization of LEDs, Crosslinking of the Polymers According to the Invention:

LEDs were produced using the general process outlined below. In individual cases, of course, this had to be adapted to the respective circumstances (e.g. polymer viscosity and optimum layer thickness of the polymer in the device). The LEDs described below were each two-layer systems, i. H. ITO substrate // // // polymer PEDOT // cathode. PEDOT is a polythiophene derivative.

General procedure for the production of highly efficient, long-lasting LEDs: After the ITO-coated substrates (e.g. glass carrier, PET film) have been cut to the correct size, they are cleaned in several cleaning steps in an ultrasonic bath (e.g. soap solution, Millipore water , Isopropanol). For drying, they are blown off with an N ₂ gun and stored in a desiccator. Before coating with the polymer, they are treated with an ozone plasma device for about 20 minutes. A solution of the respective polymer (generally with a concentration of 4-25 mg / ml in, for example, toluene, chlorobenzene, xylo cyclohexanone (4: 1)) is made up and dissolved by stirring at room temperature. Depending on the polymer, it can also be advantageous to stir at 50 - 70 ° C for some time. Once the polymer has completely dissolved, it is filtered through a 5μm filter and spun on at variable speeds (400-6000) using a spin coater. The layer thicknesses can be varied in the range of approx. 50 and 300 nm. A conductive polymer, preferably doped PEDOT or PANI, is usually applied to the (structured) ITO beforehand. Electrodes are also applied to the polymer films. This is usually done by thermal evaporation (Balzer BA360 or Pfeiffer PL S 500). Then the transparent ITO electrode as the anode and the metal electrode (e.g. Ba, Yb, Ca) as the cathode are contacted and the device parameters are determined.

The results obtained with the polymers described are summarized in Part B in the table. Networking:

The crosslinking of the polymers according to the invention was achieved by the following procedure:

The polymers were in toluene solution (1.5%) with 3% by weight (based on

Polymer) photoacid (4- (thiophenoxyphenyl) diphenylsulfonium hexafluoroantimonate) was added and, as described above, spin-coated under N ₂ . To

The film was dried by irradiation with a UV lamp (10 W, 302 nm, 5th

Min) networked. The film was then annealed under N ₂ at 200 ° C for 3 minutes

(Example P1, 130 ° C for examples P2-P9) and then with a 10 ^"4 molar LiAIH ₄

Solution treated in THF.

The device data for crosslinked and uncrosslinked polymer P1 are shown in FIG. 1. The values shown here were under non-optimized conditions

(Cathode / device structure), so that the absolute values of the efficiencies are lower than in Table 1.

Verification of crosslinkability and photostructurability: A 50 nm thin film was produced from the polymer P5 mixed with photo acid (see above) and exposed through a comb structure with 200 μm prongs for 20 seconds. The film was annealed at 120 ° C for 20 seconds and the soluble part was then washed off with THF. The profile obtained with a profilometer (FIG. 2) shows good agreement with the exposed structure.

Claims

claims: 1. low molecular weight or polymeric organic materials for use in electronic applications in which at least one H atom is replaced by a group of the formula (A),

(A) where R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl, alkoxy or thioalkoxy group with 1 to 20 carbon atoms, C4-C18-aryl, C2-C10-alkenyl in which one or more hydrogens by halogen, such as Cl and F, or CN can be replaced and one or more non-adjacent C atoms can be replaced by -O-, -S-, -CO-, -COO-, -O-CO-, Z for -O-, -S-, -CO-, -COO-, -O-CO- or a bivalent group - (CR ₁ R ₂ ) _n - in which R1 and R2 independently of one another are hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group with 1 to 20 C atoms, C4-C18-aryl, C2-C10-alkenyl mean in which one or more hydrogens can be replaced by halogen, such as Cl and F or CN and one or more non-adjacent carbon atoms can be replaced by -O-, -S-, -CO-, -COO-, -O-CO-, X is a divalent group - (CR ₁ R ₂ ) _n - in which R1 and R2 independently of one another are hydrogen, a straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or thioalkoxy group with 1 to 20 C atoms, C4-C18 -Aryl, C2-C10-alkenyl mean in which one or more hydrogens can be replaced by halogen, such as Cl and F or CN, and n is an integer between 1 and 20, preferably between 3 and 10, in particular 3 or 6 , with the proviso that the number of these groups A is limited by the maximum available, ie substitutable H atoms. 2. Low molecular weight or polymeric organic materials according to claim 1, characterized in that it is electroluminescent or laser materials such as A) Homo- or copolymers based on PPV or poly-fluorene or poly-spiro B) low molecular weight compounds with 3-dimensional spirobifluorene structure, C) Low molecular weight compounds with 3-dimensional triptycene structure D) Low molecular weight compounds with a 2-dimensional triphenylene structure E) Derivatives of perylene-tetra-carboxylic acid diimide F) Derivatives of quinaciridone G) organic lanthanoid complexes H) Derivatives of aluminum tris-quinoxalinate I) oxadiazole derivatives or hole conductors such as J) polystyrenes, polyacrylates, polyamides, polyesters which carry derivatives of tetra-aryl-benzidine in the side chain, K) low molecular weight compounds with a 2-dimensional triphenylene structure or around electron conductors such as L) derivatives of aluminum tris-quinoxalinate M) oxadiazole -Derivatives. 3. Materials according to claim 2, characterized in that the content of oxethane group according to formula (A) by the molar ratio of oxetane rings based on the totality of organic rings, including the oxetane rings in the respective structure between 0.01 to Is 0.6. 4. Use of the materials according to one or more of claims 1 to 3 for the production of structured light-emitting diodes, lasers, solar cells, waveguides or integrated circuits. 5. Structured organic electronics device, with one or more active layers, at least one of these active layers being produced from one or more of the materials according to one of claims 1 to 3. 6. The device according to claim 5, characterized in that it is organic light-emitting diodes, lasers, waveguides, solar cells or organic circuits. 7. The device according to claim 5, characterized in that the active layers have different refractive indices. 8. A method for producing multilayer organic electronic device, with two or more active layers, wherein at least one of these active layers of one or more of the materials according to one of claims 1 to 3, by applying a discrete layer of the active material and its subsequent crosslinking , Application of a further active layers from one or more of the materials according to one of claims 1 to 3 and subsequent crosslinking, optionally repeating the above steps to build up the desired number of layers.